Nanocomposite materials with dynamically adjusting refractive index and methods of making the same

ABSTRACT

A concept and synthesis technology for a composite nanoparticle material which can be used to develop nanocomposite films and suspension with 1) dynamic refractive index control across a wide temperature and wavelength of light, and specified refractive index range, or 2) magnetic susceptibility or electronic conductivity over a wide temperature, magnetic field and electric field range. Core-shell nanoparticles can be made from two or more materials whose temperature dependent, electric field dependent or magnetic field dependent properties compensate one another will dynamically maintain a targeted refractive index, electronic conductivity or magnetic susceptibility over a specified temperature, electric and/or magnetic field range. Mixtures of composite nanoparticles with complementary behavior can optionally be used to widen the operational range of the nanocomposite material further or dampen temperature dependency in a controlled manner, e.g. using a non-random distribution of particles to affect a compensating gradient in the property of interest.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/018,168, filed on Dec. 31, 2007, which isincorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention is related to nanomaterials having adjustableproperties and methods of making such materials. Accordingly, thepresent invention involves the fields of nanotechnology, chemicalengineering, materials science, and physics.

SUMMARY OF THE INVENTION

A solid layered composite nanoparticle can have properties with reducedtemperature dependency. The nanoparticle can include a core and an outershell. The outer shell can include multiple layers. The core and theshell can have compositions that are different and can be chosen suchthat the composite nanoparticle exhibits a buffered temperaturedependency with respect to at least one physical property. Non-limitingexamples of physical properties include refractive index, magnetism,electrical conductivity, and combinations thereof.

Likewise, a nanoparticle film or coating can include a plurality ofnanoparticles crosslinked to a gel. The gel can include a mixture ofinorganic and organic polymers of varying flexibility. The nanoparticlescan include a core and an outer shell. The core and outer shell can havecompositions which are different and chosen so that the compositenanoparticle exhibits a buffered temperature dependency with respect toat least one physical property.

Also taught herein is a method of making a nanocomposite film coating.The coating can be made by forming a plurality of solid layeredcomposite nanoparticles having properties with reduced temperaturedependency. The formation of nanoparticles can include providing a corematerial, and forming an outer shell having one or more layers. The coreand outer shell can have compositions that are different and chosen sothat the composite nanoparticle exhibits a buffered temperaturedependency with respect to at least one physical property. The method offorming the film coating can further include forming a gel including amixture of inorganic and organic polymers of varying mechanicalflexibility, and crosslinking the nanoparticles with the gel to form ananoparticle gel. The nanoparticle gel can then be formed into a thinfilm and can coat an object.

There has thus been outlined, rather broadly, the more importantfeatures of the invention so that the detailed description thereof thatfollows may be better understood, and so that the present contributionto the art may be better appreciated. Other features of the presentinvention will become clearer from the following detailed description ofthe invention, taken with the accompanying drawings and claims, or maybe learned by the practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a is a diagram of a composite nanoparticle having three layers,A, B, and C, in accordance with one embodiment of the present invention.

FIG. 1 b is a graph illustrating the net effects of combining threematerials A, B, and C, as illustrated in FIG. 1 a, over a temperaturerange, in accordance with one embodiment of the present invention.

FIG. 1 c is a schematic of an extruder system used to form opticalfibers in accordance with one embodiment of the present invention.

FIG. 1 d is a side cut-away view of filling a mold with nanoparticlesaccordance with another embodiment of the present invention.

FIG. 1 e is a side cut-away view of annealing the filled mold of FIG. 1d.

FIG. 1 f is a side cut-away view of etching to expose tips of theannealed composite of FIG. 1 e.

FIG. 1 g is a side cut-away view of individually separated probe tipsformed in accordance with the process of FIGS. 1 d-1 f.

FIG. 2 is a bar graph illustrating the average diameter of a ZrO₂nanoparticle as a function of titration pH obtained using ammoniumhydroxide in accordance with one embodiment of the present invention.

FIG. 3 is a bar graph illustrating the average diameter of a ZrO₂/SiO₂nanoparticle as a function of number of repeated ZrO₂ and SiO₂ coatingsat pH 6 in accordance with an embodiment of the present invention.

FIG. 4 is a graph of refractive index of a glass mounted silicate gelLangmuir-Blodget thin film containing a high concentration of ZrO₂/SiO₂nanopartices (˜50% w/v) as a function of temperature in accordance withan embodiment of the present invention. Error bars represents theuncertainty of the measurement based on the average of 5 repeatedmeasurement values at a given temperatures and is limited by theinstrument resolution, the thickness distribution of each successivelayer, and the temperature stability of the thermoregulation system.

DETAILED DESCRIPTION

Before the present invention is disclosed and described, it is to beunderstood that this invention is not limited to the particularstructures, process steps, or materials disclosed herein, but isextended to equivalents thereof as would be recognized by thoseordinarily skilled in the relevant arts. It should also be understoodthat terminology employed herein is used for the purpose of describingparticular embodiments only and is not intended to be limiting.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to “a particle” includes one or more of such particles,reference to “layers” includes reference to one or more of such layers,and reference to “coating” includes one or more of such steps.

Definitions

In describing and claiming the present invention, the followingterminology will be used in accordance with the definitions set forthbelow.

As used herein, “substantial” when used in reference to a quantity oramount of a material, or a specific characteristic thereof, refers to anamount that is sufficient to provide an effect that the material orcharacteristic was intended to provide. Therefore, “substantially free”when used in reference to a quantity or amount of a material, or aspecific characteristic thereof, refers to the absence of the materialor characteristic, or to the presence of the material or characteristicin an amount that is insufficient to impart a measurable effect,normally imparted by such material or characteristic.

As used herein, a plurality of items, structural elements, compositionalelements, and/or materials may be presented in a common list forconvenience. However, these lists should be construed as though eachmember of the list is individually identified as a separate and uniquemember. Thus, no individual member of such list should be construed as ade facto equivalent of any other member of the same list solely based ontheir presentation in a common group without indications to thecontrary.

Numerical data may be expressed or presented herein in a range format.It is to be understood that such a range format is used merely forconvenience and brevity and thus should be interpreted flexibly toinclude not only the numerical values explicitly recited as the limitsof the range, but also to include all the individual numerical values orsub-ranges encompassed within that range as if each numerical value andsub-range is explicitly recited. As an illustration, a numerical rangeof “about 0.6 mm to about 0.3 mm” should be interpreted to include notonly the explicitly recited values of about 0.6 mm and about 0.3 mm, butalso include individual values and sub-ranges within the indicatedrange. Thus, included in this numerical range are individual values suchas 0.4 mm and 0.5, and sub-ranges such as from 0.5-0.4 mm, from0.4-0.35, etc. This same principle applies to ranges reciting only onenumerical value. Furthermore, such an interpretation should applyregardless of the breadth of the range or the characteristics beingdescribed.

As used herein, the term “about” means that dimensions, sizes,formulations, parameters, shapes and other quantities andcharacteristics are not and need not be exact, but may be approximatedand/or larger or smaller, as desired, reflecting tolerances, conversionfactors, rounding off, measurement error and the like and other factorsknown to those of skill in the art. Further, unless otherwise stated,the term “about” shall expressly include “exactly,” consistent with thediscussion above regarding ranges and numerical data.

Embodiments of the Invention

A composite nanoparticle material that exhibits a dynamic refractiveindex control across a wide temperature and specified refractive indexrange is disclosed and described. For example, these nanoparticles canbe crosslinked at high density within a silicon-based matrix of suitableconsistency for spreading between 2 glass plates. Several optionalfeatures of the present invention can include, dynamic refractive indexcorrection as a function of temperature, uniform refractive index valuesthroughout the material at nanoscale spatial resolution, uniform andtailorable heat transfer throughout the material, tunable for anyrefractive index range, and tailorable for dispersal in a variety of gelmatrices and films. One alternative objective is to provide a materialwith gel-like behavior and a temperature-independent optical refractiveindex in the range of 1.44-1.50.

In one aspect of the invention is a core-shell nanoparticle made fromtwo or more materials whose

$\frac{\eta}{T}$

compensate one another so as to dynamically maintain a targeted physicalproperty over a specific temperature range and at specified opticaltransmission wavelengths. Such temperature ranges can include full orsub-ranges of about 3 K to about 400 K. Mixtures of compositenanoparticles with complementary temperature dependent refractive indexbehavior can be used to widen the temperature range further. Theterminal layer can also provide a chemical platform for crosslinkingnanoparticles to matrix oligomers which can be induced to gel to adesired consistency with standard gelation initiation methods. Thislayer (A), shown in FIG. 1 a, can be further modified to compensate forchanges in refractive index of the oligomeric matrix.

Composite nanoparticles can be constructed by layer-by-layer overcoatingof silicate based nanoparticles with one or more inorganic materialswith distinctively different temperature-dependent refractive indices,magnetism, electrical conductivity or other physical properties. Forexample, the absolute refractive index of synthetic fused silicate forvisible wavelengths ranges between 1.47 and 1.45 over the temperaturerange of interest, and its thermoptic coefficient exhibits significantdecrease of about 25%. As illustrated in FIG. 1 a, to compensate forthis temperature dependent change, nanoparticles (C) can be overcoatedwith a 10-100's of nanometers thick material (B or A/B) whose refractiveindex as a function of temperature increases over the same range. Suchlayers can be constructed from a range of inorganic and organic polymersand can optionally be further doped with polarizable impurities. Lightpassing through films and coatings constructed from such a particle canemerge without any apparent refraction, or optionally a predesignedrefraction profile. The conceptual schematic of an ideal nanoparticlewhere the A/B layer adequately compensates for that of the core, C, andits expected performance is shown in FIG. 1 b.

As a simplified view, the volume fraction of the each material willaffect the overall nanoparticle property. Roughly, a 50% volume fractionZrO₂ with 50% volume SiO₂ even without the layering should give arefractive index between 2 (ZrO₂) and 1.5 (silica). Layering as in thepresent invention can result in deviation from a simple summation ofrefractive indices as above. The magnitude of such a difference willdepend on the materials chosen, their respective expansion coefficients,α, and water hydration in the oxide lattices. One reason is thatrefractive index and other physical properties (e.g., magnetism,electrical conductivity) are a function of the density of material whichis dependent on the temperature dependent expansion coefficient, α. Fora pure ZrO₂ nanoparticle it will have an α that is different from ZrO₂crystal (larger) since it will be a hydrated irregular latticestructure, and as temperature changes the water content changes, etc. Ifthe ZrO₂ is coated with a layer of hydrated silicate which has its own αgoing in the opposite direction, if the silicate layer is very thick itwill act as a kind of girdle or reinforcement preventing the ZrO₂ fromexpanding or shrinking as it may normally. Thus as a function of SiO₂thickness the effective α of ZrO₂ will decrease slightly. Thus, anexcessively thick layer of SiO₂ may overcompensate the temperaturedependent refractive index change by eliminating some of the ZrO₂ core'srefractive index change mechanically or physically. Therefore, anoptimum is where the SiO₂ increasing refractive index (expansion) isquenched by the decreasing refractive index of ZrO₂ (shrinking) whichpulls the SiO₂ in, since it is covalently linked. The amount of silicatethat is needed, therefore, can be quite small.

The above example discussion creates a material that has a refractiveindex less that ZrO₂ but not quite SiO₂. To create a particle that iscloser to SiO₂, a thin layer of ZrO₂ can be coated on a silicatenanoparticle. This means the expanding SiO₂, with decreasing refractiveindex will be boxed in by a thin layer of ZrO₂, thus quenching thetemperature dependent refractive index change. Although the discussionis directed at refractive index, other physical properties can belikewise adjusted or altered by forming multi-layered nanoparticles.Thus, although the discussion may specify refractive index, it should berecognized that likewise principles equally apply for other physicalproperties, such as, e.g., magnetism and electrical conductivity.

Optionally, a porous silicate nanoparticle core can be created by mixinga surfactant with silicate, then calcining the surfactant at 500° C. orextracting it away using hot ethanol or chloroform to clear the pores,and then infusing the pores with ZrO₂, and allowing it to solidify. Thiscan provide more intimate contact, and less likelihood of spalling thana non-porous core with layers coated thereon. Good impregnation of theZrO₂ into the silicate particles pores can affect performance. ZrO₂ issoluble in very acidic conditions, whereas silicate is not dissolved inacid. Silicates typically dissolve in basic conditions.

If layer B or A/B's of FIG. 1 a, or likewise a shell including three ormore layers, temperature dependent refractive index does notsufficiently compensate for that of A's over the entire temperaturerange and at a transmission wavelength of interest, a mixture of severaltypes of C@B and C@A/B composite nanoparticles with differentcompositions can be dispersed throughout the gel. In this manner, thegel can be used to form thin films.

The outermost or terminal layer (A) can optionally have a dual functionof additional compensation and a chemical platform for crosslinkingthese nanoparticles to short oligomers which can be further condensed toform a gel. Cross linking of the active nanoparticle elements to thegelled oligomers can significantly reduce nanoparticle leaching andeliminate unwanted phase separation of the nanoparticles from the matrixat the glass/gel interface in the melt or film formation stage. Theseevents can change the gel's optical properties and cause itsdelamination from the objects onto which it is coated or the film isplaced, such as supporting glass interfaces. One significant advantageof the proposed approach is that it can be used for very thin films,even nanometers thick, since the oligomer backbone that carries thenanoparticles can easily be crosslinked directly to the glass or othersupporting substrate or object. When used in a thin film coating,thicknesses from about 30 nm to about 30 μm are broadly typical, withabout 250 nm to about 600 nm being particularly suitable for opticalcoatings.

The nanoparticles of the present invention can be embedded in a suitablematrix which can depend on the particular application. Non-limitingexamples of matrix materials can include gels, ceramics, semiconductors,plastics, reinforced plastics, and the like. Ceramics mixed withessentially glass nanoparticle reinforcements can achieve the hardnessof ceramics with the optical clarity of glass. Similarly, suspensionscan be formed with the nanoparticles dispersed in a dispersant, e.g.,silicone oil, mineral oil, other organic or inorganic solvents. Electro-or solution-deposited semiconductor and/or ceramic materials can also besuitable. Semiconductor matrices can be useful in photonic circuitry.Synthetic opals can be metal nanoparticles surrounded by silicate orsilicate nanoparticle with some dopant arranged in an ordered array. Thenanoparticles can be embedded in a suitable matrix to form a thin filmcoating, optical fiber, or other suitable material as described in moredetail herein.

A high nanoparticle concentration in the gel, can affect the oligomericgel's elastic modulus significantly, so an optimal matrix compositioncan be designed in light of this knowledge. Depending on the processingrequirements for film formation, an optimized mixture of oligomers ofvarious lengths and branching can be recommended to achieve the desiredsetting time, and final consistency. If desired, a low vapor pressurealcoholic additive can be mixed in the matrix to match the refractiveindex of layer (A).

FIG. 1 b shows the temperature independent refractive index of thenanocomposite of FIG. 1 a occurring over the range of −40 to 80° C.Spatial uniformity of the material's refractive index at selectedtemperatures can be obtained using confocal microscopy and polarizedexcitation light to look for regions enriched in nanoparticulates. Datadescribing the effect of thermal cycling on the optical and physicalintegrity of the nanocomposite gel melt, as well as that of the curedgel film can provide an indication of the resiliency and phase stabilityof this novel material during the mixing and film casting stages, and astudy of the effect of thermal cycling on an already set gel gives anidea of the potential damaging effects of dissipated heat on the opticalproperties and distribution of nanoparticle's integrity in a set gelfilm which can arise during high light flux transmissions.

The acceptable variation in properties over a given temperature rangecan depend on the application. Such studies can be utilized forimprovement and optimization of nanoparticle and nanoparticle films. Forsome applications, a percentage change of less than +/−0.0001 refractiveindex units can be required. Pure fused silica quartz goes up onlyslightly over -40 to 80° C., e.g 1.456-1.458. The precise refractiveindex and the precise temperature fluctuation can also depend on theamount of water in the structure, e.g. in a gel embodiment. Calciningthe water away from a nanoparticulate silicate changes the refractiveindex, and returning the water restores the refractive index. In thecase of nanoparticulate silicate, the lattice structure of the silicateis not crystalline (i.e. closest packed) but is an amorphous waterpacked mass. If the particles are a different kind, for instancetemperature independent magnetic susceptibility or conductivity, thenthe allowed temperature variation may be greater. Thus, in accordancewith the present invention, the temperature independence over a givenrange for a target property can be tuned to the applicationrequirements.

As noted, FIG. 1 a and FIG. 1 b illustrate a nanoparticle and relatedrefractive index over a temperature range. The same generalconfiguration can be employed to design nanoparticles with tailoredmagnetic susceptibility and/or conductivity properties over a range oftemperatures, magnetic, and electric fields.

A concept and synthesis technology for a composite nanoparticle materialwhich can be used to develop nanocomposite films and suspension with 1)dynamic refractive index control across a wide temperature andwavelength of light, and specified refractive index range, or 2)magnetic susceptibility or electronic conductivity over a widetemperature, magnetic field and electric field range. The terminal layercan also provide a chemical platform for crosslinking nanoparticles tomatrix oligomers which can be induced to gel to a desired consistencywith standard gelation initiation methods.

The described nanoparticles can be tailored for optimal dispersal in avariety of inorganic or organic elastomer or viscoelastic matrices ofsuitable consistency for spreading using spin coating combined withtemperature, magnetic or electrical field gradients to control theplacement of the nanoparticles. The nanocomposite material can befurther post processed to crosslink the material at adequate densitywithin the inorganic or organic-based matrix to form coatings and thinfilms with specified mechanical and hardness properties. Anticipatedcorollary properties resulting in such nanocomposites include a materialwith selected properties spread uniformly throughout the material atnanoscale spatial resolution, and uniform and tailorable heat transferthroughout the material.

Core-shell nanoparticles can be made from two or more materials whosetemperature dependent, electric field dependent or magnetic fielddependent properties compensate one another will dynamically maintain atargeted refractive index, electronic conductivity or magneticsusceptibility over a specified temperature, electric and/or magneticfield range. Mixtures of composite nanoparticles with complementarybehavior can be used to widen the operational range of the nanocompositematerial further.

The ability to make multilayered nanoparticles (two or more layers) withmetals and metal oxides is well documented in the literature. Presentedherein is that selection of the materials in each nanoparticles layercan be used to develop layered nanoparticles with temperatureindependent refractive index, magnetic or electronic properties.Further, such nanoparticles and their mixtures in a base viscoelastic,elastomeric or glass matrix can be used to make tailored films andcoatings for a variety of applications. The approach is expected toimprove the uniformity of the resulting optical and other properties inthe material since compensating regions will be spatially fixed atnanoscale density. Non-uniform aggregation of nanoparticles, (a commonproblem in nanocomposite blends using multiple types of nanoparticles)is therefore less of a property degrading factor. Commonly availablenanoparticle dispersion methods (e.g. surface functionalization) can beutilized to reduce aggregation problems for the described compositenanoparticles, and therefore this material has a good potential todevelop extremely high quality (high resolution) optical, magnetic orelectronic nanocomposite materials over that of current state of theart.

The multilayer composite nanoparticles concept is extended further toinclude materials with tunable magnetic or electronic propertiesnormally temperature, electric field or magnetic field dependent.Core-shell nanoparticles (core and single coating layer) of metals suchas Ag@Au or metal/metal oxides such as Au@SiO₂, Au@TiO₂, and Au@Fe₂O₃have of course been reported. In the case of metal-metal core shellnanoparticles, the composite electronic properties of the material aredifferent from the sum of the two materials in part due to the highelectrical conductivity and lattice mismatch between the two layers.Similarly, it is noted that the optical properties of noble metalnanoparticles coated with an oxide layer are also changed since many ofthe optical properties of nanoparticles are dominated by surface states(dangling bonds and oxidation centers) that are eliminated once theoxide coating has covalently bonded. The composite nanoparticlesdescribed herein can include separating the adjacent layers with anappropriate intervening insulating layer, or selecting the ordering oflayers in such a manner so that each active layer operates in apredictable if not independent manner from other layers nearby. In thisway, tailorable temperature dependent magnetic susceptibility orelectronic properties of the particles is achieved. Such a more complexembodiment may be a nanoparticle containing multiple metal, metal oxideand organic layers arranged in an optimal order.

The nanoparticles, gels, films, and fibers of the present invention canbe used in a wide variety of applications including, but not limited to,temperature independent refractive index films for CRT screens,precision optical components; coatings for automotive windshields;coatings for windows used in thermoelectrically cooled photodetectors;coatings for optical elements used in finer optics communication relaystations at high altitudes and extremely cold environments (e.g.Antarctic, North Pole); nanosized optical lenses for lithography, nearfield scanning probe microscopy, and microchip identification; magneticdisk storage devices; chemical and biological sensor magnetic arrays;nanoscale magnetic field generators in microfluidic devices; highresolution electrically conductive touch pads; gradient field electronicfield generators for microfluidic devices; coatings for electronicdevices with tunable dielectric breakdown; conductive nanocompositecomponents for electronic devices; coatings for microresonators, lasercavities; and the like.

Films and coatings according to the present disclosure are particularlyfitting for use with optical displays, such as those used in videoscreens, and in harsh environments. The films described herein may alsobe utilized with flexible or other solar panels screens to get maximumlight input regardless of the temperature. Additionally, it should benoted that films and coatings according to the present disclosure can beformed to include a degree of flexibility, which greatly increases thepotential applications of such a coating. Flexibility can be imparted bythe molecular weight and structure of polymers included in the film. Thepolymers can also have some unique dη/dT that can be modified bychanging the structure of the polymer and the way the polymer interactswith the nanoparticle. The dη/dT increases with an increase in thedegree of organic polymerization, which increases M_(w) and branching.One way to view this is that refractive index depends on the coefficientof thermal expansion, and this coefficient depends on how the moleculesin the material give as temperature is increased, or pack when it isdecreased. Thinking of increasing temperatures first the higher theM_(w) or branching number the more entanglements and number of physicalinteractions (vanderwalls, ionic etc.) exist. So they tend to reduce theamount of expansion possible as temperature increases. Therefore thereis less refractive index change. Considering decreasing temperatures,there will be more shrinkage as the temperature is decreased as theM_(w) goes up. However there is a range where this will be true, if theM_(w) is very high, and the temperature change is fast, there is notenough time for the molecule to rearrange, relax, and so they may quenchthe shrinking altogether. In this case, the rate of temperature changebecomes important. Exactly how severe these effects are on the nanoscaledepends on how the polymer is connected to and interacting with thenanoparticle (a brush versus a flat layer). The overall effect on netrefractive index will then depend on volume fraction of polymer versusnanoparticles. As a general guideline, a nanoparticle having a smallerd₁/dT can be achieved with higher proportions of silicate within thenanoparticles. Further, generally an increase in nanoparticle volumefraction in a matrix can result in a decrease in apparent refractiveindex of the nanoparticles. If the density of nanoparticles within thecone varies as you approach the apex of a fiber probe tip then thiscould be important.

The nanoparticles of the present invention can also be used to createtemperature independent light conduits consistent with the principlealready discussed. One specific embodiment is to make an improvednear-field scanning optical microscopy (NSOM) fiber optic. Currentfibers are drawn from silicate to a 50 nm point and light is trapped inthem. Thus, the tip gets hot, and the refractive index changesaccordingly. A fiber made from nanoparticles of the present inventionembedded in glass can get hot but would have less refractive indexchange meaning the transmission of energy into the specimen through thefiber would be substantially the same regardless of temperature. Thus,this would reduce or avoid concerns about temperature calibration ofmeasurements. An NSOM fiber can either be straight or cantilevered nearthe end, but must be tapered severely to a point, i.e. tip of a cone,that is essentially the size of a single nanoparticle described here.The tip of the cone can only fit one nanoparticle, and so the tip radiusis defined by the geometry of the one nanoparticle. For light topropagate through all the nanoparticles in the cone, they have to becemented together with a material that does not cause light substantialloss (i.e. be refractive index-matched). Since the temperature gradientmoving to the tip of the cone is quite steep during use, the temperaturecompensating ability of the nanoparticles can change smoothlyapproaching the cone tip. Usually the hotter it is the more therefractive index will change, so more highly dη/dT compensatingparticles can be embedded in the hot regions (e.g. nearer the tip), andlower dη/dT compensating nanoparticles in the cooler regions (e.g.remote from the tip) to have a net high light throughput.

In one aspect of the present invention, outer shell layers, e.g. the3^(rd) or 4^(th) layers, can also function as a mechanical element, toallow or prevent the nanoparticles from forming large gaps between them.If the particles expand too much stress cracks can form. These outerlayers can typically follow the general temperature dependence of thenanoparticles, have minimal effect on refractive index (e.g. if theirvolume fraction is small), and be elastic to accommodate the maximumdimension swings that could happen.

Thus, one embodiment of the present invention can include a gradientnanocomposite fiber, where a set of nanoparticles is arrangednon-randomly to compensate for optical changes caused bytemperature/heat transfer gradients. In particular, the type andconcentration of nanoparticles can be adjusted as described herein, tobuffer or otherwise control the dη/dT of the fiber. One specific exampleapplication of such fibers is in lithography where the NSOM tip can beused as a kind of pencil or marking instrument. In another aspect of thegradient fiber is that the toughness of the tip can be increased despitethe fact it is getting thinner, by changing the nature of the outershell layers, e.g. 3^(rd) and 4^(th) layers, so that the particles arecemented together more tightly at the tip where there are fewerparticles and less tightly where the fiber is thicker. Such toughnesscan determine the overall flexibility of the probe and whether the probecan be pressed hard or not. This is an important part of getting highresolution images, and affects whether you damage the specimen byscraping the cantilever over it. The principles of the present inventionalso allow formation of combination scanning tunneling microscopy (STM)and NSOM tips (which do not currently exist to the knowledge of theinventors). With nanoparticles that are conductive, but also transparentto the particular light frequency, and also temperature compensating,the electrical conductivity can be maintained, and at the same timeachieve an optical throughput. In such a case, how these parameterschange with temperature can be controlled along the fiber length andespecially toward the cone tip. Cantilevered NSOM probes arecommercially provided to have a certain resonant frequency. This is afactor of the thickness of the fiber, the angle of the bend, and thetaper angle as the tip of the cone is approached. The above concept of ananoparticle gradient can be applied to thin films as well to reduceloss of light at interfaces, which can have temperature gradients.

Suitable tapered nanocomposite fibers can be formed using any number ofapproaches. Two exemplary approaches include extrusion followed bylocalized laser heating to form a tip end and molding/etching processes.FIG. 1 c illustrates an extrusion process which can optionally be usedto obtain a controlled nanoparticle distribution in the final fiber. Anextruder 10 can include a feed of molten matrix material 12. The feedcan optionally include a first type of nanoparticle. An optional secondtype of nanoparticle can be introduced into the molten fiber by acomputer controlled mixing port 14. This mixing port can be used toadjust the proportion of each type of nanoparticle along the length ofthe fiber. For example, the graded fiber can be formed by periodicchanges to form enriched regions having the desired nanoparticles fortapered tips. An extruded product 16 is then pulled from the extruderwhich product can then be cooled. The tapered tips can then be formed byheating the enriched regions of the fiber (e.g. having the desired tipnanoparticle content) using electrical heating or laser, for example. Asthe enriched region is heated, the fiber softens and can be pulled. Asthe diameter reduces, a neck area forms which eventually breaks to formtwo tips. This approach works well for silicate glass and polymershaving suitable viscosity and sufficient non-elasticity to preventdeformation of the tip upon breaking at the neck region.

FIGS. 1 d-1 g illustrate a second alternative approach to forming tipsfor NSOM probes.

FIG. 1 d shows depositing nanoparticles 20 into layers within recesses22 formed in a mold material 24. The mold material can be any suitablematerial such as a plastic, ceramic, glass, or other material which isnon-adherent to the nanoparticles. The particles can be deposited, forexample, by vapor or aerosol processes. As shown in FIG. 1 e, thedeposited nanoparticles can then be annealed at a temperature sufficientto allow the particles to blend with a matrix material which was alsodeposited, e.g. as a distinct layer or simultaneously with thenanoparticles, to form annealed cones 26. Silicone polymer is oneparticular example of a matrix material for such embodiments, althoughothers can be used as described previously. At higher temperatures thelayers of adjacent nanoparticles can blend to make the entire coneshaped volume solid. The mold material 24 can be left in place as partof the probe which is at least partially etched to exposed the tips 28as shown in FIG. 1 f. The individual probes 30 can be cut apart by asuitable method, e.g. laser, dicing, etc., as shown in FIG. 1 g, forintegration into a suitable device.

As noted, the nanoparticles discussed herein can be used to developnanocomposite suspensions, films, and fibers with 1) dynamic refractiveindex control across a wide temperature and wavelength of light,specified refractive index range, and over a specified dimension or 2)magnetic susceptibility or electronic conductivity over a widetemperature, magnetic field, electric field range, and specifieddimension. Core-shell nanoparticles can be made from two or morematerials whose temperature dependent, electric field dependent ormagnetic field dependent properties compensate one another willdynamically maintain a targeted refractive index, electronicconductivity or magnetic susceptibility over a specified temperature,electric and/or magnetic field range. Mixtures of compositenanoparticles with complementary behavior can be used to widen theoperational range of the nanocomposite material further.

In one aspect, the core and outer shell (single or multi-layered) can becomposed of materials independently selected from a solid metal oxide,metal, or polymer. In one embodiment, the core can comprise or consistof a pure metal or an oxide from the group IIA, IIB, IVB, VB, VIB, VIIB,VIIIB, IB, IIB, IIIA, IVA and VA metals or combinations thereof. In oneembodiment, the outer shell can include at least one layer thatcomprises or consists of a pure metal or an oxide from the group IIA,IIB, IVB, VB, VIIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA metalsdifferent from that of the core.

Although not intended to be limiting, in one aspect, the nanoparticlehas a diameter of about 1 nm to about 300 nm. In a further aspect, thenanoparticle has a diameter of about 20 nm to about 50 nm. The outershell can optionally include one or more layers which are each up to 100nm thick.

Optionally, the core and outer shell, including any layers within theouter shell, can be covalently bonded to adjacent layers. In one aspect,the covalent bonding between layers is of the form selected from thegroup consisting of direct, via homofunctional linker, viaheterofunctional linker, and combinations thereof, wherein the homo andthe hetero independently include bi and trifunctional crosslinkers. Inone aspect, the bi and trifunctional crosslinkers can include functionalgroups NH₂, SH₂, SCN, OH, COOH, TiO₃, SiO₃ and PO₄, and combinationsthereof. Further, at least some of the multiple layers of the outershell, in one aspect, consist of an organic polymer covalently bonded toadjacent underlying and overlying oxide or metal layers. In such a case,the organic polymer layer can be optionally selected from the groupconsisting of optically active polymers, conductive polymers,viscoelastic polymers, elastomers, and combinations thereof. In oneaspect, the organic polymer layer can be a viscoelastic polymer. Inanother embodiment, the organic polymer layer can be an optically activepolymer. In another embodiment, the organic polymer layer can be aconductive polymer. In still another embodiment, the organic polymerlayer can be an elastomer. In one aspect, the terminating layer of thenanoparticle shell can be a polymer. Examples of suitable polymersinclude, but are not limited to, viscoelastic: poly methymethacrylate,poly phenelene sulfide, poly phenylene oxide, polyvinylidene chloride,polycarbonate; optically active: phenyl substitutedpoly(p-phenylenevinylene, polyaramids, (pregnenolonemethacrylate)-b-poly[(dimethylamino)ethyl methacrylate] andpoly(pregnenolone methacrylate-co-methyl methacrylate; electroactive:poly(tetrafluoroethylene), poly 2-acrylamido-2-methylpropane sulfonicacid; elastomers: polysilicones, polyvinyl acetate and block copolymerconfigurations of these.

Various materials can be included in the nanoparticle. In one aspect,the core or shell or both core and shell can be is doped with an organicdye. Where the shell includes multiple layers, one or more layers can bedoped with an organic or inorganic dye. In one aspect, the organic dyecan be a ruthenium or lanthanide-based dye. A wide variety of dyes canbe suitable. As a general guideline, the choice of dye can be based onthe application. For example, if conductivity is desirable a metal baseddye can be used, since many of them allow electron transfer before theyemit light. If light emission is desired an all organic dye can besuitable though they have a tendency to self quench if the concentrationis too high, or if the dye is packed too tight. Hydrazide dyes such asCascade Blue, Pyrene, Fluorescein, Rhodamine, Luminol and others areseveral non-limiting examples.

Optionally, the nanoparticle can undergo post-processing. In one aspect,one or more of the multiple layers of the outer shell can be modified byat least one post processing methods selected from the group consistingof heat, gamma irradiation, chemical reaction, and combinations thereof.In another embodiment, some of the multiple layers of the outer shellcan include repeating layers. In a further embodiment, some of therepeating layers can be mesoporous, having been synthesized in thepresence of a surfactant which self-assembles into nanosized structures(e.g. cylinders, worms, bilayers, micelles, etc.) on the surface of theforming nanoparticle. The mesopourous layers can be configured fordeposition of metal oxide or pure metal. Non-limiting examples ofsurfactants include quarternary ammonium, alkyl silane, alkyl titanate,alkyl phosphate, or alkyl silicate surfactant, and combinations thereof.The molar ratio between the inorganic and the surfactant can be adjustedalong with an overall concentration can facilitate successful formationof such mesoporous layers as described in more detail in U.S. Pat. No.6,913,825, entitled “Process for Making Mesoporous Silicate NanoparticleCoating and Hollow Mesoporous Silica Nano-shells,” which is incorporatedhere by reference in its entirety.

In one aspect, the composite nanoparticle can be configured so as toexhibit substantially no, or tunable refractive index or reflectivitychange as a function of external temperature. In another embodiment, thecomposite nanoparticle can be configured so as to exhibit bufferedrefractive index change as a function of wavelength of light in the oneor more of the regions of the UV, visible or infrared spectrums, whereinthe buffered refractive index change is substantially free or free ofchange as a function of wavelength, and the buffered temperatureindependency is optional.

Optionally, the core material and repeating layers are selected from thegroup consisting of IIA, IIB, IVB, VB, VIIB, VIIB, VIIIB, IB, IIB, IIIA,IVA and VA elements, their oxides, and combinations thereof, such thatthe composite nanoparticles exhibit temperature or electric fieldindependent or tunable diamagnetism or ferromagnetism.

As noted, the nanoparticles discussed herein can be utilized to form athin film or bulk solid such as within a gel or glass. Optionally, athin film can be formed including spin coating. In a further embodiment,the spin coating can occur in the presence of a magnetic field gradient.Alternatively, the thin film can be prepared as an indexable thin filmby site selective binding of the nanoparticles to a lithographicallyetched or printed plate and overcoating with inorganic or organicpolymer protective coating. Nanoparticles can include a layer ofmolecules, e.g. a termination layer, which can make chemicalinteractions with a polymer matrix of a gel which can tighten or looseninteractions via attractive or repulsive van der Waals interactions.Although the concentration of nanoparticles can vary per application,the nanoparticles can generally be present from about 95 vol % to about20 vol % of the material. Generally, when total nanoparticles arepresent at less than about 20%, there is insufficient quantity toeffectively influence material properties.

Different nanoparticles can be utilized to form a single coating. In oneaspect, nanoparticles having two or more different compositions areincluded in a single coating. The proportion of each nanoparticle canvary considerably depending on the desired final properties of thematerial.

EXAMPLES Example 1 Refractive Index

The refractive index of a composite material can be estimated using oneof several theoretical models. The simplest approach is to use therelationship: η_(tota)=x_(A)η_(A)+x_(B)η_(b) where 1=x_(A)+x_(B) toobtain a composite refractive index as a function of volume fractioncomposition at a given temperature. This approach assumes that themixture of the two materials does not change the intrinsic refractiveindex of each. In reality for a nanocomposite particle the layering ofmaterials can affect the refractive of each as a result of latticemismatch which can change the density of the material from what it mightbe in its bulk state. For a material consisting of a core of material Aand a single layer of B, this can be generally expressed asη=x_(A)η_(A)+x_(B)η_(b) +F where F is a correction that accounts for thechange in density of layer , which varies with the thickness. A possiblemanifestation of the term F for a single coating layer of component B isfor example

$F_{B} = {\sum\limits_{d}{x_{B}\frac{\left( {\rho_{B} - \rho_{A}} \right)}{\rho_{A}}\eta_{B}^{{- d}/D}}}$

where the normal density of material A is increased or decreased by thefractional difference in material densities of the two materials. As thedistance away from the interface increases, the correction shoulddecrease exponentially, and the material will eventually possess anormal refractive index. The change in refractive index over thethickness of this layer depends of the nanoparticles size, since forsmall nanoparticles the high surface curvature adds additional strain tothe overlying material lattice. For large particles, the surface isrelatively flat, and only the intrinsic density difference plays adominant role. The average refractive index of this layer may thus beslightly larger or smaller than the bulk refractive index of thematerial. Each successive layer will have its own average refractiveindex that depends on the layer composition, thickness, density andrefractive index change, and so the average particle refractive index isthe average of refractive indices of each layer appropriately accountingfor their ordering (e.g. which material is the substrate for the other),their thickness, and the number of each layer.

To obtain a similar material with unchanging refractive index as afunction of temperature, a similar set of equations involving

$\frac{\eta}{T}$

is needed. In this case the temperature dependent correction for thematerial B layer must include an expression for the temperaturedependent density change of each material via the temperature dependentcompressibility, α.

Using these equations, it is possible to predict the temperaturedependent refractive index change of each material and how it isaffected by temperature, the size of the nanoparticles, the thickness ofeach repeating layer, and its composition. It is also possible tocombine this information and predict the temperature dependentrefractive index properties of a composite nanoparticle with more thantwo repeating layers by summing over, and averaging the refractive indexof each layer as described. To generate a nanoparticle with unchangingrefractive index as a function of temperature each layer may be selectedsuch that some of the layers possess a positive change in refractiveindex with temperature (including corrections for particle size andlayer thickness), and others a negative change in refractive index withtemperature (including corrections for particle size and layerthickness). The average value of all layers should result in anunchanged value of refractive index over a finite temperature range.

Example 2 Synthesis of Multilayered Zro₂/Sio₂ Nanoparticles forTemperature Dependent Refractive Index Property

ZrO₂ powder obtained from Sigma Aldrich was dissolved in aqua regia (40%HNO₃/40% H₂SO₄, 20% water overnite (˜0.5 mg/L). The resulting solutionwas opaque at a pH below 1. Nanoparticles of ZrO₂ were obtained bytitrating the solution with microliter quantities of 5M NaOH or 5M NH₃OHsolution prepared in water. Nanoparticles size was controlled by theconcentration of ZrO₂ and the pH of the titrated solution. In generalhigher concentrations of ZrO₂ lead to uncontrolled aggregation ofnanoparticles at pH values near neutral, which concentration less than 1mM produced nanoparticle suspensions. For a given concentration of ZrO₂the extent of reaction (growth of nanoparticles could be manipulated bystopping the titration at various pH values between pH 5 and 8 as shownin FIG. 2. However much improved size control should be obtained by alsomanipulating the total amount of ZrO₂ so that the reaction goes tocompletion at whatever is the terminating pH. This approach has thebenefit of reducing the amount of unreacted material left over, avoidingthe need to remove it by dialysis and reducing the danger of slowcoalescence of the nanoparticles.

ZrO₂ nanoparticles were coated with silicate, by adding tetramethoxysilane to a rapidly magnetically stirred ZrO₂ suspension at roomtemperature. The amount of tetramethoxy silane used was calculated fromthe estimated surface area of the ZrO₂ nanoparticles in the suspension(calculated from light scattering average diameter estimate). Thetetramethoxysilane was added in portions corresponding to 1 nm layersilicate coverage to avoid excessive concentration of unreacted silicatewhich could lead to aggregation of particles. While it is impossible toavoid the nucleation of solid silicate particles altogether particularlyat acidic pH, restriction of the average concentration of these ions atall times biases toward their precipitation onto existing seeds of ZrO₂nanoparticles. After sufficient silicate was added to form a 20 nm thicklayer, additional ZrO₂ solution was added to the stirring suspension.The sudden drop in suspension pH has the benefit of sweeping away anyunreacted silicate monomers by precipating them onto nearby seedparticles. The pH was readjusted to compensate for the additional aquaregia solvent and to begin the process of ZrO₂ precipitation onto theseed particles. FIG. 3 shows nanoparticle diameter as a function oflayers at pH of 6.

The refractive index of a ZrO₂/SiO₂ nanoparticle made from 10 repeatingZrO₂ and SiO₂ layers was measured using a Bausch & Lomb refractometerwith temperature controlled sample stage capable of measurement from 10to 60° C. The results are shown in FIG. 4. Samples of nanoparticles wereprepared by vacuum drying 20 ml nanoparticles suspension to concentratethe nanoparticles and then resuspending them by mild sonication for 10minutes in a small volume (200 microliters) of viscous silicone oil. Thesample was spread on the refractometer imaging glass and allowed toequilibrate to the sample holder temperature for about 10 minutes beforemeasurement.

It is to be understood that the above-referenced arrangements areillustrative of the application for the principles of the presentinvention. Numerous modifications and alternative arrangements can bedevised without departing from the spirit and scope of the presentinvention while the present invention has been shown in the drawings anddescribed above in connection with the exemplary embodiment(s) of theinvention. It will be apparent to those of ordinary skill in the artthat numerous modifications can be made without departing from theprinciples and concepts of the invention as set forth in the claims.

1. A solid layered composite nanoparticle having properties with reducedtemperature dependency, comprising: a core and an outer shell, whereinthe outer shell includes multiple layers, and wherein said core and saidouter shell have compositions which are different and chosen such thatthe composite nanoparticle exhibits a buffered temperature dependencywith respect to at least one physical property, said physical propertyselected from the group consisting of refractive index, magnetism,electrical conductivity, and combinations thereof.
 2. The nanoparticlein claim 1, wherein each of the core and outer shell, including anylayers within the outer shell, are covalently bonded to adjacent layers.3. The nanoparticle in claim 2, where the covalent bonding betweenlayers is of the form selected from the group consisting of direct, viahomo, via hetero, and combinations thereof, wherein the homo and thehetero independently include bi and trifunctional crosslinkers whichinclude functional groups NH₂, SH₂, SCN, OH, COOH, TiO₃, SiO₃, PO₄, orcombinations thereof.
 4. The nanoparticle in claim 1, wherein at leastsome of the multiple layers of the outer shell consist of an organicpolymer covalently bonded to adjacent underlying and overlying oxide ormetal layers.
 5. The nanoparticle in claim 4, wherein the organicpolymer layer is selected from the group consisting of optically activepolymers, conductive polymers, viscoelastic polymers, elastomers, andcombinations thereof.
 6. The nanoparticle in claim 1, wherein at leastone of the core and the multiple layers of the outer shell is doped witha dye.
 7. The nanoparticle in claim 6, wherein the organic dye is alanthanide-based dye.
 8. The nanoparticle in claim 1, wherein at leastone of the multiple layers of the outer shell is doped with transitionmetal ligand complexes made from elements from rows 4 and 5 of theperiodic table.
 9. The nanoparticle in claim 1, wherein one or more ofthe multiple layers of the outer shell is modified by at least one postprocessing methods selected from the group consisting of heat, gammairradiation, chemical reaction, and combinations thereof.
 10. Thenanoparticle in claim 1, wherein some of the multiple layers of theouter shell include repeating layers that are mesoporous, having beensynthesized in the presence of a surfactant which self-assembles intonanosized structures on the surface of the core nanoparticle or itssucceeding layers and wherein the repeating mesoporous layers areconfigured for deposition of metal oxide or pure metal.
 11. Thenanoparticle in claim 1, wherein the core and outer shell are selectedsuch that the composite nanoparticle exhibits substantially norefractive index or reflectivity change as a function of externaltemperature
 12. A concentrated nanoparticle suspension comprising thenanoparticle of claim 1 in silicone oil, mineral oil, or other inorganicor organic solvent.
 13. The nanoparticle in claim 1, wherein the corematerial and repeating layers are selected from the group consisting ofIIA, IIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA and VA elements,their oxides, and combinations thereof, such that the compositenanoparticles exhibit temperature or electric field independent ortunable diamagnetism or ferromagnetism.
 14. A nanocomposite thin filmcoating, comprising a plurality of nanoparticles crosslinked to a gelcomprising a mixture of polymers of varying flexibility, saidnanoparticles comprising a core and an outer shell, wherein said coreand said outer shell have compositions which are different and chosensuch that the composite nanoparticle exhibits a buffered temperaturedependency with respect to at least one physical property, said physicalproperty selected from the group consisting of refractive index,magnetism, and electrical conductivity, and combinations thereof. 15.The thin film coating of claim 14 prepared as an indexable thin film bysite selective binding of the nanoparticles to a lithographically etchedor printed plate and overcoating with a polymer protective coating. 16.The thin film coating of claim 14, wherein the gel comprises a mixtureof inorganic and organic polymers of varying magnetic dipole strengthand conductivity.
 17. The thin film coating of claim 14, wherein the gelis formed in the presence of a magnetic or electric field gradient suchthat the buffered temperature dependency is a gradient.
 18. The thinfilm coating of claim 14, wherein the plurality of nanoparticles vary incomposition so as to form a gradient in temperature dependency acrossthe thin film.
 19. A method of making a nanocomposite thin film coating,comprising: forming a plurality of solid layered composite nanoparticleshaving properties with reduced temperature dependency, said forming aplurality of nanoparticles comprising: providing a core particle;forming an outer shell having one or more layers, wherein said core andsaid outer shell have compositions which are different and chosen suchthat the composite nanoparticle exhibits a buffered temperaturedependency with respect to at least one physical property selected fromthe group consisting of refractive index, magnetism, electricalconductivity, and combinations thereof forming a gel including a mixtureof inorganic and organic polymers of varying mechanical flexibility;crosslinking the plurality of nanoparticles with the gel to form ananoparticle gel; forming the nanocomposite thin film of thenanoparticle gel by coating an object.
 20. The method of claim 19,further comprising mixing at least two composite nanoparticlecollections of the solid layered composite nanoparticles, each having adifferent composition from the other so as to achieve a target physicalproperty.
 21. The method of claim 19, wherein the thin film is formed bya liquid phase deposition or vapor phase deposition process.
 22. Themethod of claim 19, wherein the thin film is formed by spin coating. 23.The method of claim 19, wherein the thin film is formed by siteselective binding of the nanoparticles to a lithographically etched orprinted plate and overcoating with inorganic or organic polymerprotective coating.
 24. A nanocomposite optical probe, comprising aplurality of nanoparticles embedded in an optical probe matrix having atapered tip, said nanoparticles comprising a core and an outer shell,wherein said core and said outer shell have compositions which aredifferent and chosen such that the composite nanoparticle exhibits abuffered temperature dependency with respect to at least one physicalproperty, said physical property selected from the group consisting ofrefractive index, magnetism, and electrical conductivity, andcombinations thereof.
 25. The optical probe of claim 24, wherein theouter shell includes multiple layers having different compositions. 26.The optical probe of claim 24, wherein the optical probe is an opticalNSOM fiber.
 27. The optical probe of claim 24, wherein the plurality ofnanoparticles exhibit a dη/dT gradient across the optical probe,sufficient to produce a buffered temperature having a lower dη/dT at thetapered tip than remote from the tapered tip.